Molecular tectonics — Use of urethanes and ureas derived from tetraphenylmethane and tetraphenylsilane to build porous chiral hydrogen-bonded networks

2004 ◽  
Vol 82 (2) ◽  
pp. 386-398 ◽  
Author(s):  
Dominic Laliberté ◽  
Thierry Maris ◽  
James D Wuest
Keyword(s):  
Hydrogen Bonding ◽  
Asymmetric Catalysis ◽  
Crystal Engineering ◽  
Three Dimensional ◽  
Enantiomerically Pure ◽  
X Ray ◽  
Molecular Tectonics ◽  
X Ray Crystallography ◽  
Open Networks ◽  
Hydrogen Bonded

Tetraphenylmethane, tetraphenylsilane, and simple derivatives with substituents that do not engage in hydrogen bonding typically crystallize as close-packed structures with essentially no space available for the inclusion of guests. In contrast, derivatives with hydrogen-bonding groups are known to favor the formation of open networks that include significant amounts of guests. To explore this phenomenon, we synthesized six new derivatives 5a–5e and 6a of tetraphenylmethane and tetraphenylsilane with urethane and urea groups at the para positions, crystallized the compounds, and determined their structures by X-ray crystallography. As expected, all six compounds crystallize to form porous three-dimensional hydrogen-bonded networks. In the case of tetraurea 5e, 66% of the volume of the crystals is accessible to guests, and guests can be exchanged in single crystals without loss of crystallinity. Of special note are: (i) the use of tetrakis(4-isocyanatophenyl)methane (1f) as a precursor for making enantiomerically pure tetraurethanes and tetraureas, including compounds 5b, 5c; and (ii) their subsequent crystallization to give porous chiral hydrogen-bonded networks. Such materials promise to include chiral guests enantioselectively and to be useful in the separation of racemates, asymmetric catalysis, and other applications.Key words: crystal engineering, molecular tectonics, hydrogen bonding, networks, porosity, urethanes, ureas, tetraphenylmethane, tetraphenylsilane.

Manifestations of noncovalent bonding in the solid state. 6. [H4(cyclam)]4+ (cyclam = 1,4,8,11-tetraazacyclotetradecane) as a template for crystal engineering of network hydrogen-bonded solids

1995 ◽  
Vol 73 (3) ◽  
pp. 414-424 ◽  
Author(s):  
S. Subramanian ◽  
Michael J. Zaworotko
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Engineering ◽  
Water Molecules ◽  
Crystal Data ◽  
Large Excess ◽  
X Ray ◽  
X Ray Crystallography ◽  
Noncovalent Bonding ◽  
Perchlorate Salt ◽  
Hydrogen Bonded

A series of salts of composition [H4(cyclam)]X•nH2O, where cyclam = 1,4,8,11-tetraazacyclotetradecane and X = 4Cl− (1−, n = 4), 4Br− (2, n = 4), 4I− (3, n = x), 4ClO4−(4, n = 2), 4CNS− (5, n = 2), 2SO42−(6, n = 6), and (p-CH3C6H4SO3−) (7, n = 0) have been prepared and crystal structures of 1, 2, 4, 5, 6, and 7 have been determined by single crystal X-ray crystallography. 1, 2, 3, 4, and 7 were prepared by crystallizing cyclam with a large excess of the corresponding acid whereas the thiocyanate, 5, and the sulphate, 6, salts were prepared by metathesis of the perchlorate salt, 4, with KCNS and K2SO4, respectively. Crystal data: 1: orthorhombic, Pnnb, a = 7.7962(16), b = 14.278(4), c = 17.787(4) Å, V = 1979.9(8) Å3, Z = 4, Dc = 1.39 Mg m−3, Rf = 0.051, and Rw = 0.069 for 1176 reflections with I > 3σ(I). 2: triclinic. [Formula: see text]a = 7.6860(8), b = 7.8848(9), c = 9.6385(11) Å, α = 105.111(16)°, β = 95.495(18)°, γ = 102,464(17)°, V = 543.43(12) Å3, Z = 1, Dc = 1 1.82 Mg m−3,Rf = 0.034, and Rw = 0.041 for 1530 reflections with I > 3σ(I). 4: monoclinic, P21/n, a = 8.4519(11), b = 15.9248(12), c = 9.2981(17) Å, β = 106.243(18)°, V = 1201.5(3) Å3, Z = 2, Dc, = 1.76 Mg m−3, Rf = 0.052, and Rw = 0.068 for 1902 reflections with I > 3.0σ(I). 5: triclinic, [Formula: see text] a = 8.2996(7), b = 9.0061(15), c = 9.2015(15) Å, α = 107.60(3)°, β = 97.738(14)°, γ = 108.863(9)°, V = 599.44(15) Å3, Z = 1, Dc = 1.309 Mg m−3Rf = 0.038 and Rw = 0.049 for 1856 reflections with I > 4σ(I). 6: triclinic, [Formula: see text] a = 7.8687(5), b = 8.8396(12), c = 9.0405(25) Å, α = 68.547(16), β = 85.332(9), γ = 78.473(7)°, V = 573.43(18) Å3, Z = 1, Dc = 1.693 Mg m−3, Rf = 0.053 and Rw = 0.076 for 1441 reflections with I > 3σ(I). 7: triclinic, [Formula: see text] a = 8.533(3), b = 9.110(3), c = 15.3605(21) Å, α = 82.475(17)°, β = 74.307(20)°, γ = 73.26(3)°, V = 1099.0(5) Å3, Z = 1, Dc = 1.343 Mg m−3, Rf = 0.042 and Rw = 0.052 for 2460 reflections with I > 2.5σ(I). 1, 2, 4, 5, 6, and 7 exhibit extensive network hydrogen bonding between the anions, cations, and, if appropriate, water molecules of crystallization. The dimensionality of the hydrogen-bonded networks is dependent upon the nature of the anion and the number of water molecules of crystallization since the cation adapts a centrosymmetric exodentate conformation in all six salts. Keywords: crystal engineering, cyclams, network hydrogen bonding.

scholarly journals Molecular Recognition in Proton-Transfer Compounds of Brucine with Achiral Substituted Salicylic Acid Analogues

2006 ◽  
Vol 59 (5) ◽  
pp. 320 ◽  
Author(s):  
Graham Smith ◽  
Urs D. Wermuth ◽  
Peter C. Healy ◽  
Jonathan M. White
Keyword(s):  
Proton Transfer ◽  
Three Dimensional ◽  
Water Molecules ◽  
Sulfosalicylic Acid ◽  
X Ray ◽  
X Ray Crystallography ◽  
Guest Species ◽  
Substituted Benzoic Acids ◽  
Proton Transfer Compounds ◽  
Hydrogen Bonded

The 1:1 proton-transfer brucinium compounds from the reaction of the alkaloid brucine with 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, and 5-sulfosalicylic acid, namely anhydrous brucinium 5-nitrosalicylate (1), brucinium 3,5-dinitrosalicylate monohydrate (2), and brucinium 5-sulfosalicylate trihydrate (3) have been prepared and their crystal structures determined by X-ray crystallography. All structures further demonstrate the selectivity of brucine for meta-substituted benzoic acids and comprise three-dimensional hydrogen-bonded framework polymers. Two of the compounds (1 and 3) have the previously described undulating brucine sheet host-substructures which incorporate interstitially hydrogen-bonded salicylate anion guest species and additionally in 3 the water molecules of solvation. The structure of 2 differs in having a three-centre brucinium–salicylate anion bidentate N+–H···O(carboxyl) hydrogen-bonding association linking the species through interstitial associations involving also the water molecules of solvation. A review of the crystallographic structural literature on strychnine and brucine is also given.

Sulfur as hydrogen-bond acceptor in cocrystals of 2-thio-modified thymine

2018 ◽  
Vol 74 (1) ◽  
pp. 21-30 ◽  
Author(s):  
Wilhelm Maximilian Hützler ◽  
Michael Bolte
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Crystal Engineering ◽  
Rational Design ◽  
Three Dimensional ◽  
Good Reliability ◽  
Hydrogen Bond Acceptor ◽  
Hydrogen Bonding Interactions ◽  
Hydrogen Bonding Site ◽  
Hydrogen Bonded

Doubly and triply hydrogen-bonded supramolecular synthons are of particular interest for the rational design of crystal and cocrystal structures in crystal engineering since they show a high robustness due to their high stability and good reliability. The compound 5-methyl-2-thiouracil (2-thiothymine) contains an ADA hydrogen-bonding site (A = acceptor and D = donor) if the S atom is considered as an acceptor. We report herein the results of cocrystallization experiments with the coformers 2,4-diaminopyrimidine, 2,4-diamino-6-phenyl-1,3,5-triazine, 6-amino-3H-isocytosine and melamine, which contain complementary DAD hydrogen-bonding sites and, therefore, should be capable of forming a mixed ADA–DAD N—H...S/N—H...N/N—H...O synthon (denoted synthon 3s N·S;N·N;N·O), consisting of three different hydrogen bonds with 5-methyl-2-thiouracil. The experiments yielded one cocrystal and five solvated cocrystals, namely 5-methyl-2-thiouracil–2,4-diaminopyrimidine (1/2), C5H6N2OS·2C4H6N4, (I), 5-methyl-2-thiouracil–2,4-diaminopyrimidine–N,N-dimethylformamide (2/2/1), 2C5H6N2OS·2C4H6N4·C3H7NO, (II), 5-methyl-2-thiouracil–2,4-diamino-6-phenyl-1,3,5-triazine–N,N-dimethylformamide (2/2/1), 2C5H6N2OS·2C9H9N5·C3H7NO, (III), 5-methyl-2-thiouracil–6-amino-3H-isocytosine–N,N-dimethylformamide (2/2/1), (IV), 2C5H6N2OS·2C4H6N4O·C3H7NO, (IV), 5-methyl-2-thiouracil–6-amino-3H-isocytosine–N,N-dimethylacetamide (2/2/1), 2C5H6N2OS·2C4H6N4O·C4H9NO, (V), and 5-methyl-2-thiouracil–melamine (3/2), 3C5H6N2OS·2C3H6N6, (VI). Synthon 3s N·S;N·N;N·O was formed in three structures in which two-dimensional hydrogen-bonded networks are observed, while doubly hydrogen-bonded interactions were formed instead in the remaining three cocrystals whereby three-dimensional networks are preferred. As desired, the S atoms are involved in hydrogen-bonding interactions in all six structures, thus illustrating the ability of sulfur to act as a hydrogen-bond acceptor and, therefore, its value for application in crystal engineering.

Preparation of Rhenium Diamino Dithiolate Complexes. The X-Ray Crystal Structure of Oxo(1,1,8,8-tetraethyl-3,6-diazaoctane-1,8-dithiolato)rhenium

1993 ◽  
Vol 46 (7) ◽  
pp. 1093 ◽  
Author(s):  
TW Jackson ◽  
M Kojima ◽  
RM Lambrecht
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Intermolecular Hydrogen Bonding ◽  
X Ray ◽  
X Ray Crystallography ◽  
Dithiolate Complexes ◽  
Hydrogen Bonded

The complexes oxo (1,1,8,8-tetraethyl-3,6-diazaoctane-1,8-dithiolato)rhenium[ ReO ( tedadt )], oxo (1,1,8,8-tetraethyl-4,4-dimethyl-3,6-diazaoctane-1,8-dithiolato)rhenium [ ReO ( tedmdadt )] and (1,1,4,4,8,8-hexamethyl-3,6-diazaoctane-1,8-dithiolato) oxorhenium [ ReO ( hmdadt )] were prepared. The crystal structure of the complex ReO ( tedadt ) was determined by X-ray crystallography to be a hydrogen-bonded dimer . This is the first example of intermolecular hydrogen bonding in rhenium diamino dithiolate ( dadt ) complexes.

Rage Against Conformity: Ruthenium(ɪɪ) Bisterpyridine Complexes Respond to Crystal Engineering Instructions with Whelming Results

2017 ◽  
Vol 70 (5) ◽  
pp. 529 ◽  
Author(s):  
Hasti Iranmanesh ◽  
Kasun S. A. Arachchige ◽  
William A. Donald ◽  
Niamh Kyriacou ◽  
Chao Shen ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Solid State ◽  
Single Crystal ◽  
Crystal Engineering ◽  
Intermolecular Hydrogen Bonding ◽  
Hydrogen Bond Donor ◽  
One Dimensional ◽  
X Ray ◽  
Hydrogen Bonded

Four heteroleptic ruthenium(ii) complexes of 4′-functionalised 2,2′:6′,2′′-terpyridine are reported, along with their solid-state single-crystal X-ray structures. The complexes feature complementary hydrogen-bond donor (phenol) and acceptor (pyridyl) groups designed to assemble into one-dimensional polymers. In one example, the system obeys the programmed instructions to form a one-dimensional, self-complementary hydrogen-bonded polymer. In one other example, a water-bridged hydrogen-bonded polymer is formed. In the remaining two structures, aryl–aryl interactions dominate the intermolecular interactions, and outweigh the contribution of intermolecular hydrogen bonding.

Inclusion Compounds of Thiourea and Peralkylated Ammonium Salts. VI. Hydrogen-Bonded Host Lattices Constructed From Thiourea and Anions of Oxalic Acid and Fumaric Acid

1997 ◽  
Vol 53 (2) ◽  
pp. 252-261 ◽  
Author(s):  
Q. Li ◽  
T. C. W. Mak
Keyword(s):  
Crystal Structure ◽  
Three Dimensional ◽  
Water Molecules ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Single Column ◽  
Host Lattices ◽  
Type Crystal ◽  
Hydrogen Bonded

New inclusion complexes tetra-n-butylammonium hydrogen oxalate–thiourea (1/2), (n-C4H9)4N+.HC2O4 −.2[(NH2)2CS] (1), tetramethylammonium hydrogen fumarate–thiourea (1/1), (CH3)4N+.HC4H2O4 −.(NH2)2CS (2), di(tetraethylammonium) fumarate–thiourea (1/2), [(C2H5)4N+]2.C4H2O4 2−.2[(NH2)2CS] (3) and tetra-n-propylammonium hydrogen fumarate–thiourea–water (1/1/2), (n-C3H7)4N+.HC4H2 O4 −.(NH2)2CS.2H2O (4) have been prepared and characterized by X-ray crystallography. Crystal data, Mo Kα radiation: (1), space group P21/n, a = 8.854 (6), b = 9.992 (3), c = 32.04 (2) Å, β = 97.34 (3), Z = 4, R F = 0.055 for 2261 observed data; (2), space group P\overline 1, a = 6.269 (2), b = 8.118 (4), c = 14.562 (8) Å, α = 104.79 (4), β= 91.72 (4), γ = 101.30 (4)°, Z = 2, R F = 0.078 for 1543 observed data; (3), space group P21/n, a = 11.340 (2), b = 9.293 (6), c = 14.619 (2) Å, β = 102.41 (2)°, Z = 2, R F = 0.050 for 1856 observed data; (4), space group P2/n, a = 16.866 (4), b = 8.311  (1), c = 17.603 (2) Å, β = 104.94 (1)°, Z = 4, R F = 0.048 for 2785 observed data. In the crystal structure of (1) the tetra-n-butylammonium ions are sandwiched between puckered layers, which are constructed from thiourea-hydrogen oxalate ribbons. In the crystal structure of (2), zigzag O--H...O and C--H...O hydrogen-bonded hydrogen fumarate ribbons are linked by thiourea dimers to form a wide puckered ribbon and the crystal structure is built of a packing of these thiourea–anion composite ribbons and the cationic columns. In the layer-type crystal structure of (3) a series of thiourea–fumarate layers match the (002) planes and the (C2H5)4N+ cations occupy the intervening space. In the crystal structure of (4) the thiourea, hydrogen fumarate ions and water molecules are connected by hydrogen bonds to form wide puckered ribbons, which are crosslinked to generate a three-dimensional host framework containing open channels aligned parallel to the a axis, with the tetra-n-propylammonium cations accommodated in a single column within each channel.

Formation and Structural Characterization of [RuCl2(CO)2(SPh2)2], [RuCl2(CO)3(OH2)], and [Ru(OH2)6][RuCl3(CO)3]2 · 2H2O

2003 ◽  
Vol 58 (10) ◽  
pp. 959-964 ◽  
Author(s):  
Marjaana Taimisto ◽  
Raija Oilunkaniemi ◽  
Risto S. Laitinen ◽  
Markku Ahlgrén
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Room Temperature ◽  
Three Dimensional ◽  
Temperature Reaction ◽  
X Ray ◽  
X Ray Crystallography ◽  
Dimensional Network ◽  
Moderate Yield

While the room temperature reaction of [RuCl2(CO)3]2 and Ph2S in tetrahydrofuran in air affords [RuCl2(CO)2(SPh2)2] (1) in moderate yield, that in dichloromethane results in the formation of a mixture of [RuCl2(CO)3(H2O)] (2) and [Ru(H2O)6][RuCl3(CO)3]2·2H2O (3). Very small amounts of 1 are produced only upon prolonged reflux of the reagents. All compounds were characterized by X-ray crystallography. 1 crystallizes as discrete octahedral cis(CO), cis(Cl), trans(Ph2S) complexes, which are joined into stacks by weak H···Cl hydrogen bonds. 2 is also composed of discrete octahedral complexes. Four hydrogen bonds involving aqua and chlorido ligands link two complexes into a dimer. The structure of 3 consists of octahedral hexaaquaruthenium cations and two tricarbonyltrichloridoruthenate anions. The water of crystallization is involved in hydrogen bonding between the cations and anions resulting in the formation of a continuous three-dimensional network.

Polysulfonylamine, CXXVII [1] Wasserstoffbrücken in kristallinen Onium-dimesylamiden: Ein robustes Achtring-Synthon als Bestandteil dreidimensionaler Wasserstoffbrückenmuster / Polysulfonylamines, CXXVII [1] Hydrogen Bonding in Crystalline Onium Dimesylamides: A Robust Eight-Membered Ring Synthon as a Component in Three-Dimensional Hydrogen Bonding Patterns

2000 ◽  
Vol 55 (8) ◽  
pp. 753-762 ◽  
Author(s):  
Karna Wijaya ◽  
Oliver Moers ◽  
Dagmar Henschel ◽  
Armand Blaschette ◽  
Peter G. Jones
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Engineering ◽  
Three Dimensional ◽  
Membered Ring ◽  
Monoclinic Space Group ◽  
X Ray ◽  
Secondary Bonds ◽  
Onium Salts ◽  
Crystal Packings ◽  
Bonding Patterns

Abstract In order to study crystal packings and hydrogen bonding frameworks, low-temperature X-ray structures were determined for three onium salts of general formula B H+(MeSO2)2N−, where BH+ is acetamidinium (1, monoclinic, space group P21/c, Z = 4), guanidinium (2, monoclinic, P21/c, Z = 4), or 4,6-diamino-2-thioxo-2,3-dihydropyrimidinium (3, monoclinic P21/n, Z = 4). In every case the ions create three-dimensional N − H ∙∙∙ N/O networks, in which all N − H donors of the cations and four (in 1) or five (2, 3) acceptors of the anion are involved; non-conventional secondary bonds, e.g. C − H ∙∙∙ O/N, do not play an important role in the packings. For the isotypic structures 1 and 2, congruencies and dissimilarities of the hydrogen bonding patterns are discussed in detail. Despite the structural and chemical differences between the cations and the way in which they are attached to the anion, each of the three structures displays a robust eight-membered ring synthon [N2 = R22(8), antidromic] constructed via two-centre hydrogen bonds from a syn, syn-sequence H − N − C (sp2) −N −H of the respective cation and a V-shaped O − S (sp3) − N fragment of the anion. Although the networks in 2 and 3 contain several N − H (∙∙∙ O)2 three-centre interactions, the two-point connectivity of the synthon is distinctly preserved. The results indicate that the (MeSO2)2N− ion may be utilized in crystal engineering as a dependable building block.

Encapsulation of ferrocenes by hydrogen-bonded pyrogallol[4]arene dimers

2018 ◽  
Vol 73 (8) ◽  
pp. 597-600
Author(s):  
Bei Wang ◽  
Ai-Quan Jia ◽  
Hong-Mei Yang ◽  
Jing-Long Liu ◽  
Qian-Feng Zhang
Keyword(s):  
Hydrogen Bonding ◽  
Single Crystal ◽  
Molar Ratio ◽  
Reaction Conditions ◽  
X Ray ◽  
X Ray Crystallography ◽  
Capsule Type ◽  
Hydrogen Bonding Networks ◽  
Hydrogen Bonded

AbstractThe treatment of C-iso-butylpyrogallarene (PgC4) or C-ethylpyrogallarene (PgC2) with ferrocene (FcH) in a 2:1 molar ratio under different reaction conditions afforded the host–guest compounds FcH@(PgC4)2·CH3OH·3H2O (1) and FcH@(PgC2)2·3EtOH·2H2O (2), respectively. Complexes 1 and 2 are both pyrogallarene dimers providing capsule-type voids. Single crystal X-ray crystallography was used to investigate the role of hydrogen bonding networks in the assembly of the two host–guest systems.

Solid-state and gas-phase structures of two conformers of N-(4-methylphenyl)-N′,N′′-bis(morpholinyl) phosphoric triamide; insights from X-ray crystallography and DFT calculations

2011 ◽  
Vol 67 (3) ◽  
pp. 238-243 ◽  
Author(s):  
Khodayar Gholivand ◽  
Hamid Reza Mahzouni
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Dft Calculations ◽  
Gas Phase ◽  
Bond Critical Point ◽  
X Ray ◽  
X Ray Crystallography ◽  
Equal Chance ◽  
Phosphoric Triamide ◽  
Hydrogen Bonded

A phosphoric triamide with the formula (4-CH3—C6H4NH)P(O)(NC4H8O)2 has been synthesized and characterized. X-ray crystallography at 120 K reveals that the title compound is composed of two symmetrically independent molecules in the solid state. Density functional theory (DFT) calculations reveal that two conformers A and B are very close to each other from an energy point of view. Thus there is equal chance that the presence of two conformers in the lattice may lead to hydrogen-bonded chains with an ABABAB arrangement. Hydrogen bonds of the type OP...H—N (OP being the phosphoryl O atom) are established between the two conformers with binding energies of −18.8 and −20.3 kJ mol−1 (at B3LYP/6–31+G*). The electronic delocalization LP(OP) → σ*(N—H), LP(OP) being the lone pair of OP, leads to a decrease in the strength of the N—H bond during hydrogen bonding between the conformers. The charge density (ρ) at the bond critical point (b.c.p.) of N—H decreases by ∼ 0.012–0.014 e Å–3 when the molecule participates in hydrogen bonding. This may explain the red shift of the ν(N—H) stretching frequency from a single molecule in the gas phase to a hydrogen-bonded one in the solid state.

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